US6352576B1 - Methods of selectively separating CO2 from a multicomponent gaseous stream using CO2 hydrate promoters - Google Patents
Methods of selectively separating CO2 from a multicomponent gaseous stream using CO2 hydrate promoters Download PDFInfo
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- US6352576B1 US6352576B1 US09/538,704 US53870400A US6352576B1 US 6352576 B1 US6352576 B1 US 6352576B1 US 53870400 A US53870400 A US 53870400A US 6352576 B1 US6352576 B1 US 6352576B1
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- gaseous stream
- hydrate
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- multicomponent gaseous
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical class C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the field of this invention is selective absorption of CO 2 gas.
- Syngas is a mixture of hydrogen, carbon monoxide and CO 2 that is readily produced from fossil fuels and finds use both as a fuel and as a chemical feedstock.
- the carbon monoxide is converted to hydrogen and additional CO 2 via the water-gas shift process. It is then often desirable to separate the CO 2 from the hydrogen to obtain a pure H 2 stream for subsequent use, e.g. as a fuel or feedstock.
- CO 2 As man made CO 2 is increasingly viewed as a pollutant, another area in which it is desirable to separate CO 2 from a multicomponent gaseous stream is in the area of pollution control. Emissions from industrial facilities, such as manufacturing and power generation facilities, often include CO 2 . In such instances, it is often desirable to at least reduce the CO 2 concentration of the emissions. The CO 2 may be removed prior to combustion in some cases and post combustion in others.
- a variety of processes have been developed for removing or isolating a particular gaseous component from a multicomponent gaseous stream. These processes include cryogenic fractionation, selective adsorption by solid adsorbents, gas absorption, and the like.
- gas absorption processes solute gases are separated from gaseous mixtures by transport into a liquid solvent.
- the liquid solvent ideally offers specific or selective solubility for the solute gas or gases to be separated.
- Gas absorption finds widespread use in the separation of CO 2 from multicomponent gaseous streams.
- a host solvent e.g. monoethanolamine
- removal of CO 2 from the host solvent e.g. by steam stripping
- compression of the stripped CO 2 for disposal e.g. by sequestration through deposition in the deep ocean or ground aquifers.
- Patents disclosing methods of selectively removing one or more components from a multicomponent gaseous stream include: U.S. Pat. Nos. 3,150,942; 3,359,744; 3,479,298; 3,838,553; 4,253,607; 4,861,351; 5,397,553; 5,434,330; 5,562,891; 5,600,044 and 5,700,311.
- Methods are provided for the selective removal of CO 2 from a multicomponent gaseous stream to provide a CO 2 depleted gaseous stream having at least a reduction, e.g. 20%, in the concentration of CO 2 relative to the untreated multicomponent gaseous stream.
- the multicomponent gaseous stream is contacted with an aqueous fluid, e.g. CO 2 nucleated (or structured) water, under conditions of selective CO 2 clathrate formation to produce a CO 2 clathrate slurry and CO 2 depleted gaseous stream.
- an aqueous fluid e.g. CO 2 nucleated (or structured) water
- CO 2 hydrate promoter is employed, where the CO 2 hydrate promoter is included in the multicomponent gaseous stream and/or the aqueous fluid.
- the CO 2 hydrate promoter serves to reduce the minimum CO 2 partial pressure required for formation of CO 2 containing hydrates (i.e. CO 2 hydrates) as compared to a control using pure CO 2 gas and water.
- the subject methods find use in a variety of applications where it is desired to selectively remove CO 2 from a multicomponent gaseous stream.
- Methods are provided for the selective removal of CO 2 from a multicomponent gaseous stream to provide a CO 2 depleted gaseous stream having at least a reduction, e.g. 30 to 90%, in the concentration of CO 2 relative to the untreated multicomponent gaseous stream.
- the multicomponent gaseous stream is contacted with an aqueous fluid, e.g. CO 2 nucleated (or structure) water, under conditions of selective CO 2 clathrate formation to produce a CO 2 clathrate slurry and CO 2 depleted gaseous stream.
- an aqueous fluid e.g. CO 2 nucleated (or structure) water
- a feature of the subject invention is that a CO 2 hydrate promoter is employed, where the CO 2 hydrate promoter is included in the multicomponent gaseous stream and/or the aqueous fluid.
- the CO 2 hydrate promoter serves to reduce the minimum CO 2 partial pressure required for formation of CO 2 containing hydrates as compared to a control using pure CO 2 and water.
- the subject methods find use in a variety of applications where it is desired to selectively remove CO 2 from a multicomponent gaseous stream.
- the subject invention provides a method of selectively removing CO 2 from multicomponent gaseous stream, where a feature of the subject methods is the use of a CO 2 hydrate promoter.
- the CO 2 hydrate promoter may be present in the multicomponent gaseous stream and/or in CO 2 nucleated or non-nucleated water (hydrate precursor solution).
- the first step is to provide a multicomponent gaseous stream that includes a CO 2 hydrate promoter and/or an aqueous fluid, e.g. CO 2 nucleated or non-nucleated water (water source), that includes a CO 2 hydrate promoter.
- a multicomponent gaseous stream and/or CO 2 nucleated water source is provided that includes an amount of a CO 2 hydrate promoter that is sufficient to reduce the CO 2 partial pressure requirement of hydrate formation under a given set of conditions, e.g. at or near 0° C., as compared to a control.
- CO 2 partial pressure requirement of hydrate formation is meant the CO 2 partial pressure in the multicomponent gaseous stream that is required for CO 2 hydrate formation to occur upon contact with an aqueous fluid under a given set of conditions, such as the ones described in greater detail, infra.
- the amount of CO 2 hydrate promoter that is present in the multicomponent gaseous stream and/or CO 2 nucleated water is generally sufficient to provide for a reduction in the CO 2 partial pressure requirement of hydrate formation of at least about 20%, usually at least about 30% and more usually at least about 60% as compared to a control (i.e.
- the CO 2 partial pressure requirement of hydrate formation in the absence of the CO 2 hydrate promoter under otherwise identical conditions where in certain embodiments the magnitude of the reduction may be as great as 85, 90 or 95% or more.
- the CO 2 partial pressure requirement at 0° C. in the presence of a sufficient amount of CO 2 hydrate promoter is less than about 9 atm, usually less than about 5 atm and may be as low as 2 atm or 1 atm or lower.
- the specific amount of gaseous CO 2 hydrate promoter that is present in the provided multicomponent gaseous stream of this first step depends, in large part, on the nature of the multicomponent gaseous stream, the nature of the CO 2 hydrate promoter, and the like, where representative amounts for different types of representative multicomponent gaseous streams are provided infra.
- the amount of CO 2 hydrate promoter that is present, initially, in the multicomponent gaseous stream ranges from about 1 to 5 mole percent, usually from about 1.5 to 4 mole percent and more usually from about 2 to 3 mole percent.
- the specific amount of liquid CO 2 hydrate promoter, dissolved in the CO 2 nucleated water (hydrate precursor solution) depends, in large part, on the nature of the specific dissolved liquid or solid in the nucleated water stream, the nature of the CO 2 hydrate promoters, and the like, where representative amounts for different types of representative dissolved liquid or solid hydrate promoters are provide infra.
- the amount of dissolved CO 2 promoter that is present in the nucleated water stream ranges from about 10 ppm to 10,000 ppm, usually from about 100 ppm to 2000 ppm and more usually from about 150 ppm to 1500 ppm.
- CO 2 hydrate promoter Any convenient gaseous CO 2 hydrate promoter that is capable of providing the above described reduction in CO 2 partial pressure requirement of hydrate formation when present in the multicomponent gaseous stream may be employed.
- suitable CO 2 hydrate promoters are low molecular weight compounds that have low vapor pressures at their hydrate formation pressure.
- low vapor pressure is meant a vapor pressure ranging from about 0.1 to 1 atm, usually from about 0.2 to 0.95 atm and more usually from about 0.25 to 0.92 atm.
- low molecular weight is meant a molecular weight that does not exceed about 350 daltons, usually does not exceed about 100 daltons and more usually does not exceed about 75 daltons.
- gaseous CO 2 hydrate promoter is a sulfur containing compound, where specific sulfur containing compounds of interest include: H 2 S, SO 2 , CS 2 and the like.
- H 2 S it is generally present in the multicomponent gaseous stream in an amount ranging from about 1.0 to 5.0 mole percent, usually from about 1.5 to 4.0 mole percent and more usually from about 2.0 to 3.0 mole percent.
- SO 2 it is generally present in the multicomponent gaseous stream in an amount ranging from about 1.0 to 5.0 mole percent, usually from about 1.5 to 4.0 mole percent and more usually from about 2.0 to 3.0 mole percent.
- CO 2 hydrate promoters are proton donors, such as water soluble halogenated hydrocarbons, amines and the like.
- Water soluble halogenated hydrocarbons of interest are generally those having from 1 to 5, usually 1 to 4 and more usually 1 to 2 carbon atoms, where the halogen moiety may be F, Cl, Br, I etc.
- Specific halogenated hydrocarbons of interest include chloroform, ethylene chloride, carbon tetrachloride, and the like.
- the CO 2 hydrate promoter is ethylene chloride, it is generally dissolved in the nucleated water in an amount ranging from about 100 to 2500 ppm, usually from about 500 to 2000 ppm and more usually from about 1000 to 1800 ppm.
- CO 2 hydrate promoter is chloroform
- it is generally present in the nucleated water in an amount ranging from about 100 to 2500 ppm, usually from about 500 to 2000 ppm and more usually from about 1000 to 1800 ppm.
- CO 2 hydrate promoter is carbon tetrachloride
- it is generally present in the nucleated water in an amount ranging from about 50 to 200 ppm, usually from about 80 to 160 ppm and more usually from about 100 to 120 ppm.
- amines such as diethanolamine
- diethanolamine it is generally present in the nucleated water stream in an amount ranging from about 1000 to 5000 ppm, usually from about 500 to 3000 ppm and more usually from about 1000 to 3000 ppm.
- alkyl ammonium salts are compounds with cations of the generic formula:
- R usually consists of hydrocarbon elements of the formula:
- R may be methyl or normal (linear) C 4 H 9 , but may also be iso-C 3 H 11 .
- the anionic portion of the salt may consist of simple ions such as: F—, HCOO—, OH—, Br—, Cl—, NO 3 —, etc, but may also be ions such as normal (linear):
- the sulfonium salts usually are compounds with cations of the generic formula:
- R may be any of the possibilities cited above.
- all three R's need not be of the same chemical composition.
- the anion for the sulfonium salts is usually F—.
- the phosphonium salts generally have the generic formula:
- the anions may be anions as described above.
- This class of akyl-onium salts readily form hydrate structures involving encagement of the salt in the same class of polyhedral water cages as seen in the simple gas hydrates. (In many cases the anion actually is part of the cage structure.)
- the hydrates of these salts form at atmospheric pressure and are stable well above the freezing point of water (where some melting points exceed 20° C.).
- the above described “onium” salts vary widely in the number of water molecules per salt molecule (i.e. the hydration number).
- the hydration number may be as low as 4 (for hydroxide salts) and as high as 50 (for formate salts), but will typically range from about 18 to 38 (e.g. for flouride and oxalate salts).
- concentration to be used depends on which embodiment of the invention is employed. When used as a means for nucleating water, concentrations are similar to the gaseous promoters, usually in the range of 100 to 150 ppm. However, when used to form mixed hydrates, the promoter salt concentration may be substantially higher depending on the final partial pressure of CO 2 that is sought. For the “onium” salts, this could be as high as 30 wt. percent, but is more typically in the range of from 5 to 25% by wt.
- the promoter structure away from the charged end is chosen to be chemically similar to the gaseous component whose solubility is to be decreased and chosen to have an affinity for gas molecules whose solubility is to be increased. Since alteration of gaseous solubility would typically be used in conjunction with the other embodiments (e.g. formation of mixed hydrates, raising of T, or lowering of P) the concentrations could be as high as 30 wt. %, but typically would be about 5 to 25 wt. %.
- the above organic or onium salts find particular use as hydrate promoters in the following applications: (1) as a means of nucleating water so that CO 2 hydrates from for readily; (2) as a means of forming mixed hydrates of CO 2 and the alkyl-onium salts, where the mixed hydrates may consist predominantly of salt guest molecules and are useful in the final step to bring the CO 2 partial pressure down to below 1 atm; (3) as a means of raising the temperature at which CO 2 hydrates or mixed CO 2 -alkyl-onium salt hydrates will form; (4) as a means to lower the partial pressure of CO 2 required for formation of the CO 2 containing hydrates; (b) as a means to alter the solubility of gases in the process water.
- the R-groups on the cations are typically chosen so as to lower the solubility of compounds where incorporation into the CO 2 or mixed hydrate is undesirable.
- R's may be chosen as hydrocarbon moieties which lower the solubility of methane in water for natural gas upgrading gas applications.
- the R groups are chosen so that solubility of gases, whose incorporation into the hydrate is desirable, is increased.
- An example would be R groups with a mild chemical affinity for the solvated gas of interest, e.g. CO 2 .
- the nucleated water further includes a freezing point depression agent or “anti-freeze” agent.
- Frezing point depression agents that may be included in the nucleated water are glycerol, ethylene glycol, and the like.
- the amount of freezing point depressing agent that is included is generally sufficient to reduce the freezing point of the nucleated water by at least about 5, usually by at least about 10 and up to 20° C. or more. As such, the amount of freezing point depressing agent in the nucleated water typically ranges from about 20 to 30% by volume.
- the multicomponent gaseous stream may be provided in the first step of the subject invention using any convenient protocol.
- a multicomponent gaseous stream of interest will merely be tested to ensure that it includes the requisite amount of CO 2 hydrate promoter of interest.
- this step requires adding a sufficient amount of the CO 2 hydrate promoter to the multicomponent gaseous stream to be treated.
- the requisite amount of CO 2 hydrate promoter that needs to be added to a given multicomponent gaseous stream of interest necessarily varies depending on the nature of the gaseous stream, the nature of the CO 2 hydrate promoter, the desired CO 2 separation ratio and the like.
- the requisite amount of CO 2 hydrate promoter may be added to the multicomponent gaseous stream using any convenient protocol, e.g. by combining gaseous streams, recycling gaseous compounds, adding appropriate gaseous components, etc.
- the next step in the subject methods is to contact the multicomponent gaseous stream with an aqueous fluid under conditions sufficient for CO 2 hydrate formation to occur.
- aqueous fluids of interest include water, either pure water or salt water, CO 2 nucleated water as described in U.S. Pat. No. 5,700,311 and U.S. patent application Ser. Nos. 09/067,937, now U.S. Pat. No. 6,090,186 and 09/330,251, now U.S. Pat. No. 6,106,595; the disclosures of which are herein incorporated by reference, and the like.
- the aqueous fluid may include a CO 2 hydrate promoter in certain embodiments.
- Aqueous fluids such as nucleated water containing a CO 2 hydrate promoter may be prepared using any convenient protocol, e.g. by introducing an appropriate amount of the liquid CO 2 hydrate promoter to the aqueous fluid.
- the multicomponent gaseous stream to be treated according to the subject methods is contacted with water which may contain CO 2 hydrate precursors or hydrate precursors of the promoter compounds.
- the nucleated water may or may not include a CO 2 hydrate promoter, as described above.
- the CO 2 nucleated water employed in these embodiments of the subject invention comprises dissolved CO 2 in the form of CO 2 hydrate precursors, where the precursors are in metastable form. These precursors may be composite for mixed hydrates containing both CO 2 and promoter molecules
- the mole fraction of CO 2 in the CO 2 nucleated water ranges from about 0.01 to 0.10, usually from about 0.02 to 0.08, more usually from about 0.04 to 0.06.
- the temperature of the CO 2 nucleated water typically ranges from about ⁇ 1.5 to 10° C., preferably from about 0 to 5° C., and more preferably from about 0.5 to 3.0° C. In those embodiments in which an antifreeze is employed, the temperature often ranges from about ⁇ 20 to ⁇ 5° C.
- CO 2 nucleated water employed in the subject methods as the selective liquid absorbent or adsorbent may be prepared using any convenient means.
- One convenient means of obtaining CO 2 nucleated water is described in U.S. Application Ser. No. 08/291,593, filed Aug. 16, 1994, now U.S. Pat. No. 5,562,891, the disclosure of which is herein incorporated by reference.
- CO 2 is first dissolved in water using any convenient means, e.g. bubbling a stream of CO 2 gas through the water, injection of CO 2 into the water under conditions of sufficient mixing or agitation to provide for homogeneous dispersion of the CO 2 throughout the water, and the like, where the CO 2 source that is combined with the water in this first stage may be either in liquid or gaseous phase.
- the gaseous CO 2 will typically be pressurized, usually to partial pressures ranging between 6 to 50 atm, more usually between about 10 to 20 atm.
- the CO 2 may be derived from any convenient source.
- at least a portion of the CO 2 is gaseous CO 2 obtained from a CO 2 hydrate slurry decomposition step, as described in greater detail below.
- the water in which the CO 2 is dissolved may be fresh water or salt water, e.g. sea water, or may contain CO 2 hydrate promoters.
- the temperature of the CO 2 nucleated water typically ranges from about ⁇ 1.5 to 10° C., preferably from about 0 to 5° C., and more preferably from about 0.5 to 3.0° C. In those embodiments in which an antifreeze is employed, the temperature often ranges from about ⁇ 20 to ⁇ 5° C.
- the water that is used to produce the nucleated water may be obtained from any convenient source, where convenient sources include the deep ocean, deep fresh water aquifers, powerplant cooling ponds, and the like, and cooled to the required reactor conditions.
- the nucleated water may be recycled from a downstream source, such a clathrate slurry heat exchanger/decomposition source (as described in greater detail below) where such recycled nucleated water may be supplemented as necessary with additional water, which water may or may not be newly synthesized nucleated water as described above and may, or may not, contain dissolved CO 2 hydrate promoters.
- the amount of CO 2 which is dissolved in the water is determined in view of the desired CO 2 mole fraction of the CO 2 nucleated water to be contacted with the gaseous stream.
- One means of obtaining CO 2 nucleated water having relatively high mole fractions of CO 2 is to produce a slurry of CO 2 clathrates and then decompose the clathrates by lowering the pressure and/or raising the temperature of the slurry to release CO 2 and regenerate a partially nucleated water stream.
- nucleated water having higher mole fractions of CO 2 are desired because it more readily accepts CO 2 absorption or adsorption and limits formation of other hydrate compounds.
- high mole fraction of CO 2 is meant a mole fraction of about 0.05 to 0.09, usually from about 0.06 to 0.08.
- the production of CO 2 nucleated water may conveniently be carried out in a nucleation reactor.
- the reactor may be packed with a variety of materials, where particular materials of interest are those which promote the formation of CO 2 nucleated water with hydrate precursors and include: stainless steel rings, carbon steel rings, metal oxides and the like, to promote gas-liquid contact and catalyze hydrate formation.
- active coolant means may be employed. Any convenient coolant means may be used, where the coolant means will typically comprise a coolant medium housed in a container which contacts the reactor, preferably with a large surface area of contact, such as coils around and/or within the reactor or at least a portion thereof, such as the tail tube of the reactor.
- Coolant materials or media of interest include liquid ammonia, HCFCs, and the like, where a particular coolant material of interest is ammonia, where the ammonia is evaporated at a temperature of from about ⁇ 10 to ⁇ 5° C.
- the surface of the cooling coils, or a portion thereof, may be coated with a catalyst material, such as an oxide of aluminum, iron, chromium, titanium, and the like, to accelerate CO 2 hydrate precursor formation. Additionally, hydrate crystal seeding or a small (1-3 atm) pressure swing may be utilized to enhance hydrate precursor formation.
- the CO 2 nucleated water is prepared by contacting water (e.g. fresh or salt water) with high pressure, substantially pure CO 2 gas provided from an external high pressure CO 2 gas source.
- water e.g. fresh or salt water
- substantially pure CO 2 gas provided from an external high pressure CO 2 gas source.
- the water is contacted with substantially pure CO 2 gas which is at a pressure that is about equal to or slightly above the total multicomponent gaseous stream pressure.
- the pressure of the substantially pure CO 2 gas typically ranges in many embodiments from about 5 to 7 atm above the multicomponent gaseous stream pressure, and may be 15 to 80, usually 20 to 70 and more usually 25 to 60 atm above the CO 2 partial pressure of the multicomponent gaseous stream (CO 2 overpressure stimulation of hydrate precursor and hydrate formation).
- substantially pure is meant that the CO 2 gas is at least 95% pure, usually at least 99% pure and more usually at least 99.9% pure.
- Advantages realized in this preferred embodiment include the production of CO 2 saturated water that comprises high amounts of dissolved CO 2 , e.g. amounts (mole fractions) ranging from about 0.02 to 0.10, usually from about 0.04 to 0.08. Additional advantages include the use of relatively smaller nucleation reactors (as compared to nucleation reactors employed in other embodiments of the subject invention) and the production of more CO 2 selective nucleated water. In those embodiments where small nucleation reactors are employed, it may be desirable to batch produce the CO 2 saturated water, e.g.
- the CO 2 saturated water is readily converted to nucleated water, i.e. water laden with CO 2 hydrate precursors, using any convenient means, e.g. by temperature cycling, contact with catalysts, pressure cycling, etc. This prestructuring of the hydrate formation water not only increases the kinetics of hydrate formation, but also reduces the exothermic energy release in the CO 2 hydrate reactor. This, in turn, reduces the cooling demands of the process and increases overall process efficiency.
- the multicomponent gaseous stream with or without hydrate promoters is contacted with the aqueous fluid, e.g. CO 2 nucleated water with or without hydrate promoters, under conditions of CO 2 clathrate formation, preferably under conditions of selective CO 2 clathrate formation.
- the aqueous fluid may be contacted with the gaseous stream using any convenient means.
- Preferred means of contacting the aqueous fluid with the gaseous stream are those means that provide for efficient removal, e.g. by absorption or adsorption which enhances hydrate formation, of the CO 2 from the gas through solvation of the gaseous CO 2 within the liquid phase.
- Means that may be employed include concurrent contacting means, i.e.
- contact between unidirectionally flowing gaseous and liquid phase streams countercurrent means, i.e. contact between oppositely flowing gaseous and liquid phase streams, and the like.
- contact may be accomplished through use of fluidic Venturi reactor, spray, tray, or packed column reactors, and the like, as may be convenient.
- a hydrate or clathrate formation reactor contact between the multicomponent gaseous stream and the aqueous fluid is carried out in a hydrate or clathrate formation reactor.
- the reactor may be fabricated from a variety of materials, where particular materials of interest are those which catalyze the formation of CO 2 clathrates or hydrates and include: stainless steel, carbon steel, and the like.
- the reactor surface, or a portion thereof, may be coated with a catalyst material, such as an oxide of aluminum, iron, chromium, titanium, and the like, to accelerate CO 2 hydrate formation.
- active coolant means may be employed.
- coolant means may be used, where the coolant means will typically comprise a coolant medium housed in a container which contacts the reactor, preferably with a large surface area of contact, such as coils around or within the reactor or at least a portion thereof, such as the exit plenum and tail tube of the reactor.
- Coolant materials or media of interest include ammonia, HCFCs and the like, where a particular coolant material of interest is ammonia, where the ammonia is maintained at a temperature of from about ⁇ 10 to ⁇ 5° C.
- the reactor comprises gas injectors as the means for achieving contact to produce clathrates, the reactor may comprise 1 or a plurality of such injectors.
- the number of injectors will range from 1 to about 20 or more, where multiple injectors provide for greater throughput and thus greater clathrate production.
- Specific examples of various reactors that may be employed for clathrate production are provided in U.S. Application Ser. No. 09/067,937, the disclosure of which is herein incorporated by reference.
- the clathrate formation conditions under which the gaseous and liquid phase streams are contacted may vary but will preferably be selected so as to provide for the selective formation of CO 2 clathrates, limiting the clathrate formation of other components of the multi-component gaseous stream.
- the temperature at which the gaseous and liquid phases are contacted will range from about ⁇ 1.5 to 10° C., usually from about ⁇ 0 to 5° C., more usually from about 0.5 to 3.0° C.
- the total pressure of the environment in which contact occurs, e.g. in the reactor in which contact occurs may range from about 3 to 200 atm, usually from about 10 to 100 atm.
- the CO 2 partial pressure at which contact occurs generally does not exceed about 80 atm, and usually does not exceed bout 40 atm.
- the minimum CO 2 partial pressure at which hydrates form in the presence of CO 2 hydrate promoters is generally less than about 9 atm, usually less than about 5 atm and may be as low or 2 or 1 atm or lower.
- CO 2 Upon contact of the gaseous stream with the aqueous fluid, CO 2 is selectively removed from the gaseous stream and CO 2 hydrates are formed as the CO 2 reacts with the CO 2 nucleated water liquid phase containing CO 2 hydrate precursors, with or without CO 2 hydrate promoters.
- the removed CO 2 is concomitantly fixed as solid CO 2 clathrates in the liquid phase slurry.
- Contact between the gaseous and liquid phases results in the production of a CO 2 depleted multicomponent gaseous stream and a slurry of CO 2 clathrates.
- the CO 2 concentration is reduced by at least about 50%, usually by at least about 70%, and more usually by at least about 90%, as compared to the untreated multicomponent gaseous stream.
- contact of the multicomponent gaseous stream with the CO 2 nucleated water results in at least a decrease in the concentration of the CO 2 of the gaseous phase, where the decrease will be at least about 50%, usually at least about 70%, more usually at least about 90%.
- the concentration of CO 2 in the gaseous phase may be reduced to the level where it does not exceed 5% (v/v), such that the treated gaseous stream is effectively free of CO 2 solute gas.
- many embodiments of the subject methods provide for a “single-pass” efficiency of CO 2 removal of at least about 50%, and often at least about 75 or 90% or higher.
- the CO 2 removed from the multicomponent gaseous stream is concomitantly fixed in the form of stable CO 2 clathrates.
- Fixation of the CO 2 in the form of stable CO 2 clathrates results in the conversion of the aqueous fluid to a slurry of CO 2 clathrates.
- the slurry of CO 2 clathrates produced upon contact of the gaseous stream with the aqueous fluid comprises CO 2 stably fixed in the form of CO 2 clathrates and water.
- Typical mole fractions of CO 2 in stable clathrates are 0.12 to 0.15.
- the CO 2 mole fraction may be lower, in the range of 0.05 to 0.12. These lower mole fractions may be employed, particularly if a two (2) stage hydrate reactor process is utilized., wherein the concentration of hydrate promoters may be varied between the two (2) stages to enhance low CO 2 partial pressure hydrate formation, particularly in the second stage. In these cases mixed hydrates of CO 2 and the promoter liquid or salt will form and permit lower CO 2 partial pressures, as low as 1 atm or less, to form hydrates; thus increasing overall CO 2 separation ratios from the multicomponent gaseous stream.
- Methods of the subject invention generally also include the separation of the treated gaseous phase from the CO 2 clathrate slurry.
- the gaseous phase may be separated from the slurry in the reactor or in a downstream gas-liquid separator. Any convenient gas-liquid phase separation means may be employed, where a number of such means are known in the art.
- the gas-liquid separator that is employed is a horizontal separator with one or more, usually a plurality of, gas off takes on the top of the separator.
- the subject invention provides for extremely high recovery rates of the multicomponent gaseous stream. In other words, the amount of non-CO 2 gases removed from the multicomponent gaseous stream following selective CO 2 extraction according to the subject invention are extremely low.
- the amount of combustible gases (i.e. H 2 , CH 4 and CO) recovered is above 99%, usually above 99.2% and more usually above 99.5%, where the amount recovered ranges in many embodiments from about 99.6 to 99.8%.
- the resultant CO 2 clathrate slurry may be disposed of directly as is known in the art, e.g. through placement in gas wells, the deep ocean or freshwater aquifers, and the like, or subsequently processed to separate the clathrates from the remaining nucleated water, where the isolated clathrates may then be disposed of according to methods known in the art and the remaining nucleated water recycled for further use as a selective CO 2 absorbent in the subject methods, and the like.
- CO 2 gas can easily be regenerated from the clathrates, e.g. where high pressure CO 2 is to be a product or further processed for sequestration, using known methods.
- the resultant CO 2 gas may be disposed of by transport to the deep ocean or ground aquifers, or used in a variety of processes, e.g. enhanced oil recovery, coal bed methane recovery, or further processed to form metal carbonates, e.g. MgCO 3 , for fixation and sequestration.
- the CO 2 hydrate slurry is treated in a manner sufficient to decompose the hydrate slurry into CO 2 gas and CO 2 nucleated water, i.e. it is subjected to a decomposition step.
- the CO 2 hydrate slurry is thermally treated, e.g. flashed, where by thermally treated is meant that temperature of the CO 2 hydrate slurry is raised in sufficient magnitude to decompose the hydrates and produce CO 2 gas.
- the temperature of the CO 2 hydrate slurry is raised to a temperature of between about 40 to 50° F., at a pressure ranging from about 3-20 to 200 atm, usually from about 40 to 100 atm.
- One convenient means of thermally treating the CO 2 hydrate slurry is in a counterflow heat exchanger, where the heat exchanger comprises a heating medium in a containment means that provides for optimal surface area contact with the clathrate slurry.
- Any convenient heating medium may be employed, where specific heating media of interest include: ammonia, HCFC's and the like, with ammonia vapor at a temperature ranging from 20 to 40° C. being of particular interest.
- the ammonia vapor is that vapor produced in cooling the nucleation and/or hydrate formation reactors, as described in greater detail in terms of the figures.
- Multicomponent gaseous streams that may be treated according to the subject invention will comprise at least two different gaseous components and may comprise five or more different gaseous components, where at least one of the gaseous components will be CO 2 , where the other component or components may be one or more of N 2 , O 2 , H 2 O, CH 4 , H 2 , CO and the like, as well as one or more trace gases, e.g. H 2 S, SO 2 , etc.
- the total pressure of the gas will generally be at least about 15 atm, usually at least about 20 atm and more usually at least about 40 atm.
- the mole fraction of CO 2 in the multicomponent gaseous streams amenable to treatment according to the subject invention will typically range from about 0.10 to 0.90, usually from about 0.15 to 0.70, more usually from about 0.30 to 0.60 atm.
- the partial pressure of CO 2 in the multicomponent gaseous stream need not be high, and may be as low as 5 atm or lower, e.g. 2 or 1 atm or lower.
- Multicomponent gaseous streams that may be treated according to the subject methods include both reducing, e.g. syngas, shifted syngas, natural gas, and hydrogen and the like, and oxidizing condition streams, e.g. flue gases from combustion.
- Particular multicomponent gaseous streams of interest that may be treated according to the subject invention include: oxygen containing combustion power plant flue gas, turbo charged boiler product gas, coal gasification product gas, shifted coal gasification product gas, anaerobic digester product gas, wellhead natural gas stream, reformed natural gas or methane hydrates, and the like.
- Multicomponent gaseous mediums in which the partial pressures of each of the components are suitable for selective CO 2 hydrate formation according to the subject invention may be treated directly without any pretreatment or processing.
- multicomponent gaseous mediums that are not readily suitable for treatment by the subject invention e.g. in which the partial pressure of CO 2 is too low and/or the partial pressure of the other components are too high, may be subjected to a pretreatment or preprocessing step in order to modulate the characteristics of the gaseous medium so that is suitable for treatment by the subject method.
- Illustrative pretreatment or preprocessing steps include: temperature modulation, e.g. heating or cooling, decompression, compression, incorporation of additional components, e.g. H 2 S and other hydrate promoter gases, and the like.
- the subject methods and systems provide for a number of advantages.
- the subject methods provide for extremely high CO 2 removal rates and separation ratios from the multicomponent gaseous stream.
- the CO 2 separation ratio exceeds about 75%.
- the CO 2 removal rate may exceed about 90% or even 95% in many embodiments.
- These exceptional recovery rates are observed at low CO 2 partial pressures, e.g. partial pressures that are less than about 5 atm in many embodiments as low as 1 to 2 atm or lower.
Abstract
Description
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US09/538,704 US6352576B1 (en) | 2000-03-30 | 2000-03-30 | Methods of selectively separating CO2 from a multicomponent gaseous stream using CO2 hydrate promoters |
JP2001572204A JP2003528721A (en) | 2000-03-30 | 2001-03-23 | Method for selectively separating CO2 from a multi-component gas stream using a CO2 hydration promoter |
EP01924300A EP1283740A4 (en) | 2000-03-30 | 2001-03-23 | Methods of selectively separating co 2? from a multicomponent gaseous stream using co 2? hydrate promoters |
PCT/US2001/009465 WO2001074472A1 (en) | 2000-03-30 | 2001-03-23 | Methods of selectively separating co2 from a multicomponent gaseous stream using co2 hydrate promoters |
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Cited By (74)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6602326B2 (en) * | 2000-06-08 | 2003-08-05 | Korea Advanced Institute Of Science And Technology | Method for separation of gas constituents employing hydrate promoter |
US20040123738A1 (en) * | 2002-12-27 | 2004-07-01 | Spencer Dwain F. | Methods and systems for selectively separating CO2 from a multicomponent gaseous stream |
US20050120878A1 (en) * | 2003-12-04 | 2005-06-09 | Dennis Leppin | Process for separating carbon dioxide and methane |
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US7128777B2 (en) | 2004-06-15 | 2006-10-31 | Spencer Dwain F | Methods and systems for selectively separating CO2 from a multicomponent gaseous stream to produce a high pressure CO2 product |
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US20080072495A1 (en) * | 1999-12-30 | 2008-03-27 | Waycuilis John J | Hydrate formation for gas separation or transport |
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US7875163B2 (en) | 2008-07-16 | 2011-01-25 | Calera Corporation | Low energy 4-cell electrochemical system with carbon dioxide gas |
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US20110091366A1 (en) * | 2008-12-24 | 2011-04-21 | Treavor Kendall | Neutralization of acid and production of carbonate-containing compositions |
US7958731B2 (en) | 2009-01-20 | 2011-06-14 | Sustainx, Inc. | Systems and methods for combined thermal and compressed gas energy conversion systems |
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US8495872B2 (en) | 2010-08-20 | 2013-07-30 | Sustainx, Inc. | Energy storage and recovery utilizing low-pressure thermal conditioning for heat exchange with high-pressure gas |
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US8539763B2 (en) | 2011-05-17 | 2013-09-24 | Sustainx, Inc. | Systems and methods for efficient two-phase heat transfer in compressed-air energy storage systems |
US8578708B2 (en) | 2010-11-30 | 2013-11-12 | Sustainx, Inc. | Fluid-flow control in energy storage and recovery systems |
US20130337378A1 (en) * | 2012-06-15 | 2013-12-19 | Shin-Etsu Chemical Co., Ltd. | Sulfonium salt, polymer, resist composition, and patterning process |
US8667792B2 (en) | 2011-10-14 | 2014-03-11 | Sustainx, Inc. | Dead-volume management in compressed-gas energy storage and recovery systems |
US8677744B2 (en) | 2008-04-09 | 2014-03-25 | SustaioX, Inc. | Fluid circulation in energy storage and recovery systems |
US8709367B2 (en) | 2010-07-30 | 2014-04-29 | General Electric Company | Carbon dioxide capture system and methods of capturing carbon dioxide |
US8834688B2 (en) | 2009-02-10 | 2014-09-16 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
US8869477B2 (en) | 2008-09-30 | 2014-10-28 | Calera Corporation | Formed building materials |
US9133581B2 (en) | 2008-10-31 | 2015-09-15 | Calera Corporation | Non-cementitious compositions comprising vaterite and methods thereof |
US9180401B2 (en) | 2011-01-20 | 2015-11-10 | Saudi Arabian Oil Company | Liquid, slurry and flowable powder adsorption/absorption method and system utilizing waste heat for on-board recovery and storage of CO2 from motor vehicle internal combustion engine exhaust gases |
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Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JP5488573B2 (en) * | 2011-12-05 | 2014-05-14 | Jfeエンジニアリング株式会社 | Gas collecting agent and gas collecting method |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3150942A (en) | 1959-10-19 | 1964-09-29 | Chemical Construction Corp | Method of purifying a hydrogen gas stream by passing said gas in series through 13x and 4a or 5a molecular sieves |
US3359744A (en) | 1965-06-16 | 1967-12-26 | Air Prod & Chem | Hydrogen purification system with separated vapor and liquid mixed to provide a heat exchange medium |
US3479298A (en) | 1964-08-04 | 1969-11-18 | Lummus Co | Production of hydrogen |
US3838553A (en) | 1971-04-20 | 1974-10-01 | Petrocarbon Dev Ltd | Separation of mixtures especially gas mixtures |
US4235607A (en) | 1979-01-19 | 1980-11-25 | Phillips Petroleum Company | Method and apparatus for the selective absorption of gases |
US4821794A (en) * | 1988-04-04 | 1989-04-18 | Thermal Energy Storage, Inc. | Clathrate thermal storage system |
US4861351A (en) | 1987-09-16 | 1989-08-29 | Air Products And Chemicals, Inc. | Production of hydrogen and carbon monoxide |
JPH03164419A (en) | 1989-11-21 | 1991-07-16 | Mitsubishi Heavy Ind Ltd | Treatment of gaseous carbon dioxide |
US5159971A (en) * | 1991-06-27 | 1992-11-03 | Allied-Signal Inc. | Cooling medium for use in a thermal energy storage system |
US5277038A (en) * | 1992-08-28 | 1994-01-11 | Instatherm Company | Thermal storage system for a vehicle |
US5364611A (en) * | 1989-11-21 | 1994-11-15 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for the fixation of carbon dioxide |
US5397553A (en) | 1992-10-05 | 1995-03-14 | Electric Power Research Institute, Inc. | Method and apparatus for sequestering carbon dioxide in the deep ocean or aquifers |
US5434330A (en) | 1993-06-23 | 1995-07-18 | Hnatow; Miguel A. | Process and apparatus for separation of constituents of gases using gas hydrates |
US5536893A (en) * | 1994-01-07 | 1996-07-16 | Gudmundsson; Jon S. | Method for production of gas hydrates for transportation and storage |
US5600044A (en) | 1994-09-15 | 1997-02-04 | Exxon Production Research Company | Method for inhibiting hydrate formation |
US5700311A (en) * | 1996-04-30 | 1997-12-23 | Spencer; Dwain F. | Methods of selectively separating CO2 from a multicomponent gaseous stream |
US5958844A (en) * | 1997-07-25 | 1999-09-28 | Institut Francais Du Petrole | Method of transporting hydrates suspended in production effluents |
US6028234A (en) * | 1996-12-17 | 2000-02-22 | Mobil Oil Corporation | Process for making gas hydrates |
JP3164419B2 (en) | 1991-06-17 | 2001-05-08 | ハイドルクレーム コーポレイション | Method and device for measuring and blending different material components |
-
2000
- 2000-03-30 US US09/538,704 patent/US6352576B1/en not_active Expired - Fee Related
-
2001
- 2001-03-23 WO PCT/US2001/009465 patent/WO2001074472A1/en active Application Filing
- 2001-03-23 JP JP2001572204A patent/JP2003528721A/en active Pending
- 2001-03-23 EP EP01924300A patent/EP1283740A4/en not_active Withdrawn
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3150942A (en) | 1959-10-19 | 1964-09-29 | Chemical Construction Corp | Method of purifying a hydrogen gas stream by passing said gas in series through 13x and 4a or 5a molecular sieves |
US3479298A (en) | 1964-08-04 | 1969-11-18 | Lummus Co | Production of hydrogen |
US3359744A (en) | 1965-06-16 | 1967-12-26 | Air Prod & Chem | Hydrogen purification system with separated vapor and liquid mixed to provide a heat exchange medium |
US3838553A (en) | 1971-04-20 | 1974-10-01 | Petrocarbon Dev Ltd | Separation of mixtures especially gas mixtures |
US4235607A (en) | 1979-01-19 | 1980-11-25 | Phillips Petroleum Company | Method and apparatus for the selective absorption of gases |
US4861351A (en) | 1987-09-16 | 1989-08-29 | Air Products And Chemicals, Inc. | Production of hydrogen and carbon monoxide |
US4821794A (en) * | 1988-04-04 | 1989-04-18 | Thermal Energy Storage, Inc. | Clathrate thermal storage system |
US5364611A (en) * | 1989-11-21 | 1994-11-15 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for the fixation of carbon dioxide |
JPH03164419A (en) | 1989-11-21 | 1991-07-16 | Mitsubishi Heavy Ind Ltd | Treatment of gaseous carbon dioxide |
JP3164419B2 (en) | 1991-06-17 | 2001-05-08 | ハイドルクレーム コーポレイション | Method and device for measuring and blending different material components |
US5159971A (en) * | 1991-06-27 | 1992-11-03 | Allied-Signal Inc. | Cooling medium for use in a thermal energy storage system |
US5277038A (en) * | 1992-08-28 | 1994-01-11 | Instatherm Company | Thermal storage system for a vehicle |
US5397553A (en) | 1992-10-05 | 1995-03-14 | Electric Power Research Institute, Inc. | Method and apparatus for sequestering carbon dioxide in the deep ocean or aquifers |
US5562891A (en) * | 1992-10-05 | 1996-10-08 | The California Institute Of Technology | Method for the production of carbon dioxide hydrates |
US5434330A (en) | 1993-06-23 | 1995-07-18 | Hnatow; Miguel A. | Process and apparatus for separation of constituents of gases using gas hydrates |
US5536893A (en) * | 1994-01-07 | 1996-07-16 | Gudmundsson; Jon S. | Method for production of gas hydrates for transportation and storage |
US5600044A (en) | 1994-09-15 | 1997-02-04 | Exxon Production Research Company | Method for inhibiting hydrate formation |
US5700311A (en) * | 1996-04-30 | 1997-12-23 | Spencer; Dwain F. | Methods of selectively separating CO2 from a multicomponent gaseous stream |
US6028234A (en) * | 1996-12-17 | 2000-02-22 | Mobil Oil Corporation | Process for making gas hydrates |
US5958844A (en) * | 1997-07-25 | 1999-09-28 | Institut Francais Du Petrole | Method of transporting hydrates suspended in production effluents |
Non-Patent Citations (6)
Title |
---|
Austvick et al. (1992). "Deposition of CO2 On the Seabed in the Form of Hydrates" Energy Convers. Mgmt., vol. 33(5-8): 659-666. |
Golomb et al. (1992). "The Fate of CO2 Sequestered in the Deep Ocean" Energy Convers. Mgmt., vol. 33(5-8): 675-683. |
Nishikawa et al. (1992). "CO2 Clathrate Formation and its Properties in the Simulated Deep Ocean" Energy Convers. Mgmt., vol. 33(5-8): 651-657. |
Saji et al. (1992). "Fixation of Carbon Dioxide by Clathrate-Hydrate" Energy Convers. Mgmt., vol. 33(5-8): 643-649. |
Spencer (1991). "A Preliminary Assessment of Carbon Dioxide Mitigation Options" Annu. Rev. Energy Environ., vol. 16: 259-273. |
Spencer et al. (1992). "Innovative CO2 Separation and Sequestration Process for Treating Multicomponent Gas Streams" Freely Distributed by Authors Prior to Filing Date but After Apr. 28, 1997. |
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US20040123738A1 (en) * | 2002-12-27 | 2004-07-01 | Spencer Dwain F. | Methods and systems for selectively separating CO2 from a multicomponent gaseous stream |
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US7128777B2 (en) | 2004-06-15 | 2006-10-31 | Spencer Dwain F | Methods and systems for selectively separating CO2 from a multicomponent gaseous stream to produce a high pressure CO2 product |
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US20080245274A1 (en) * | 2005-02-24 | 2008-10-09 | Ramme Bruce W | Carbon Dioxide Sequestration in Foamed Controlled Low Strength Materials |
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US20070248527A1 (en) * | 2006-04-25 | 2007-10-25 | Spencer Dwain F | Methods and systems for selectively separating co2 from an oxygen combustion gaseous stream |
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US20090301352A1 (en) * | 2007-12-28 | 2009-12-10 | Constantz Brent R | Production of carbonate-containing compositions from material comprising metal silicates |
US20100135882A1 (en) * | 2007-12-28 | 2010-06-03 | Constantz Brent R | Methods of sequestering co2 |
US20100132556A1 (en) * | 2007-12-28 | 2010-06-03 | Constantz Brent R | Methods of sequestering co2 |
US20100135865A1 (en) * | 2007-12-28 | 2010-06-03 | Constantz Brent R | Electrochemical methods of sequestering co2 |
US20110059000A1 (en) * | 2007-12-28 | 2011-03-10 | Constantz Brent R | Methods of sequestering co2 |
US7887694B2 (en) | 2007-12-28 | 2011-02-15 | Calera Corporation | Methods of sequestering CO2 |
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US20110056193A1 (en) * | 2008-04-09 | 2011-03-10 | Mcbride Troy O | Systems and methods for energy storage and recovery using compressed gas |
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US20090282822A1 (en) * | 2008-04-09 | 2009-11-19 | Mcbride Troy O | Systems and Methods for Energy Storage and Recovery Using Compressed Gas |
US8763390B2 (en) | 2008-04-09 | 2014-07-01 | Sustainx, Inc. | Heat exchange with compressed gas in energy-storage systems |
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US8677744B2 (en) | 2008-04-09 | 2014-03-25 | SustaioX, Inc. | Fluid circulation in energy storage and recovery systems |
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US8240146B1 (en) | 2008-06-09 | 2012-08-14 | Sustainx, Inc. | System and method for rapid isothermal gas expansion and compression for energy storage |
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US20100239467A1 (en) * | 2008-06-17 | 2010-09-23 | Brent Constantz | Methods and systems for utilizing waste sources of metal oxides |
US20100140103A1 (en) * | 2008-07-16 | 2010-06-10 | Gilliam Ryan J | Gas Diffusion Anode and CO2 Cathode Electrolyte System |
US7875163B2 (en) | 2008-07-16 | 2011-01-25 | Calera Corporation | Low energy 4-cell electrochemical system with carbon dioxide gas |
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US20100021361A1 (en) * | 2008-07-23 | 2010-01-28 | Spencer Dwain F | Methods and systems for selectively separating co2 from a multi-component gaseous stream |
US7966250B2 (en) | 2008-09-11 | 2011-06-21 | Calera Corporation | CO2 commodity trading system and method |
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US8834688B2 (en) | 2009-02-10 | 2014-09-16 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatalytic electrodes |
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US8137444B2 (en) | 2009-03-10 | 2012-03-20 | Calera Corporation | Systems and methods for processing CO2 |
US8234868B2 (en) | 2009-03-12 | 2012-08-07 | Sustainx, Inc. | Systems and methods for improving drivetrain efficiency for compressed gas energy storage |
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US20100307156A1 (en) * | 2009-06-04 | 2010-12-09 | Bollinger Benjamin R | Systems and Methods for Improving Drivetrain Efficiency for Compressed Gas Energy Storage and Recovery Systems |
US8046990B2 (en) | 2009-06-04 | 2011-11-01 | Sustainx, Inc. | Systems and methods for improving drivetrain efficiency for compressed gas energy storage and recovery systems |
US8104274B2 (en) | 2009-06-04 | 2012-01-31 | Sustainx, Inc. | Increased power in compressed-gas energy storage and recovery |
US8479502B2 (en) | 2009-06-04 | 2013-07-09 | Sustainx, Inc. | Increased power in compressed-gas energy storage and recovery |
US20100084280A1 (en) * | 2009-07-15 | 2010-04-08 | Gilliam Ryan J | Electrochemical production of an alkaline solution using co2 |
US20110079515A1 (en) * | 2009-07-15 | 2011-04-07 | Gilliam Ryan J | Alkaline production using a gas diffusion anode with a hydrostatic pressure |
US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
US20110147227A1 (en) * | 2009-07-15 | 2011-06-23 | Gilliam Ryan J | Acid separation by acid retardation on an ion exchange resin in an electrochemical system |
US8109085B2 (en) | 2009-09-11 | 2012-02-07 | Sustainx, Inc. | Energy storage and generation systems and methods using coupled cylinder assemblies |
US8037678B2 (en) | 2009-09-11 | 2011-10-18 | Sustainx, Inc. | Energy storage and generation systems and methods using coupled cylinder assemblies |
US8468815B2 (en) | 2009-09-11 | 2013-06-25 | Sustainx, Inc. | Energy storage and generation systems and methods using coupled cylinder assemblies |
US8117842B2 (en) | 2009-11-03 | 2012-02-21 | Sustainx, Inc. | Systems and methods for compressed-gas energy storage using coupled cylinder assemblies |
US8245508B2 (en) | 2010-04-08 | 2012-08-21 | Sustainx, Inc. | Improving efficiency of liquid heat exchange in compressed-gas energy storage systems |
US8171728B2 (en) | 2010-04-08 | 2012-05-08 | Sustainx, Inc. | High-efficiency liquid heat exchange in compressed-gas energy storage systems |
US8661808B2 (en) | 2010-04-08 | 2014-03-04 | Sustainx, Inc. | High-efficiency heat exchange in compressed-gas energy storage systems |
US8191362B2 (en) | 2010-04-08 | 2012-06-05 | Sustainx, Inc. | Systems and methods for reducing dead volume in compressed-gas energy storage systems |
US8234863B2 (en) | 2010-05-14 | 2012-08-07 | Sustainx, Inc. | Forming liquid sprays in compressed-gas energy storage systems for effective heat exchange |
US8709367B2 (en) | 2010-07-30 | 2014-04-29 | General Electric Company | Carbon dioxide capture system and methods of capturing carbon dioxide |
US8495872B2 (en) | 2010-08-20 | 2013-07-30 | Sustainx, Inc. | Energy storage and recovery utilizing low-pressure thermal conditioning for heat exchange with high-pressure gas |
US8578708B2 (en) | 2010-11-30 | 2013-11-12 | Sustainx, Inc. | Fluid-flow control in energy storage and recovery systems |
US9297285B2 (en) | 2011-01-20 | 2016-03-29 | Saudi Arabian Oil Company | Direct densification method and system utilizing waste heat for on-board recovery and storage of CO2 from motor vehicle internal combustion engine exhaust gases |
US9180401B2 (en) | 2011-01-20 | 2015-11-10 | Saudi Arabian Oil Company | Liquid, slurry and flowable powder adsorption/absorption method and system utilizing waste heat for on-board recovery and storage of CO2 from motor vehicle internal combustion engine exhaust gases |
US9581062B2 (en) | 2011-01-20 | 2017-02-28 | Saudi Arabian Oil Company | Reversible solid adsorption method and system utilizing waste heat for on-board recovery and storage of CO2 from motor vehicle internal combustion engine exhaust gases |
US9371755B2 (en) | 2011-01-20 | 2016-06-21 | Saudi Arabian Oil Company | Membrane separation method and system utilizing waste heat for on-board recovery and storage of CO2 from motor vehicle internal combustion engine exhaust gases |
US8806866B2 (en) | 2011-05-17 | 2014-08-19 | Sustainx, Inc. | Systems and methods for efficient two-phase heat transfer in compressed-air energy storage systems |
US8539763B2 (en) | 2011-05-17 | 2013-09-24 | Sustainx, Inc. | Systems and methods for efficient two-phase heat transfer in compressed-air energy storage systems |
US8667792B2 (en) | 2011-10-14 | 2014-03-11 | Sustainx, Inc. | Dead-volume management in compressed-gas energy storage and recovery systems |
US20130337378A1 (en) * | 2012-06-15 | 2013-12-19 | Shin-Etsu Chemical Co., Ltd. | Sulfonium salt, polymer, resist composition, and patterning process |
US9162967B2 (en) * | 2012-06-15 | 2015-10-20 | Shin-Etsu Chemical Co., Ltd. | Sulfonium salt, polymer, resist composition, and patterning process |
CN103304479A (en) * | 2013-05-28 | 2013-09-18 | 常州大学 | Promoter for CO2 hydrate and application of promoter |
CN103304479B (en) * | 2013-05-28 | 2015-07-01 | 常州大学 | Promoter for CO2 hydrate and application of promoter |
US10183865B2 (en) * | 2016-11-25 | 2019-01-22 | Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences | Apparatus and combined process for carbon dioxide gas separation |
US11660486B1 (en) * | 2019-08-14 | 2023-05-30 | Dieter R. Berndt | Fire extinguisher and method |
US11439858B1 (en) * | 2019-08-14 | 2022-09-13 | Dieter R. Berndt | Fire extinguisher and method |
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JP2003528721A (en) | 2003-09-30 |
EP1283740A1 (en) | 2003-02-19 |
EP1283740A4 (en) | 2005-12-14 |
WO2001074472A1 (en) | 2001-10-11 |
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